Acetic Acid → HCID 12082301, compound

HRID 986990Notes

Reaction equation

HRID 986990 reaction equation
[C:1]([CH2:5][NH:6][NH2:7])([F:4])([F:3])[F:2].C([O:10][C:11]([C:13]1([CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][N:29]=2)[C:18](=O)[CH2:17][CH2:16][N:15]([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:14]1)=O)C.C(O)(=O)C>C1(C)C=CC=CC=1>[C:23]([O:22][C:20]([N:15]1[CH2:16][CH2:17][C:18]2=[N:7][N:6]([CH2:5][C:1]([F:4])([F:3])[F:2])[C:11](=[O:10])[C:13]2([CH2:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][N:29]=2)[CH2:14]1)=[O:21])([CH3:26])([CH3:24])[CH3:25]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 787402,2,2-Trifluoroethylhydrazine2×HCID 12082300HCID 12082300, compound

Product 1

HCID 12082301HCID 12082301, compoundYield 110.6%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Conditions

Temperature
70 °C

Procedure

A 70% aqueous solution of CF3CH2NHNH2 (325 mL, 1.986 mol) (obtained from Aldrich) was extracted with toluene (3×1200 mL). To a solution of the product from step A (600 g, 1.655 mol) in toluene (900 mL) was first added the combined toluene extracts containing the anhydrous 2,2,2-trifluoroethyl hydrazine, followed by acetic acid (121.4 g, 1.986 mol). The reaction mixture was heated at about 70° C. for about 2 hours, then another toluene extraction of 70% aqueous 2,2,2-trifluoroethyl hydrazine (50 g) was added. The reaction mixture was heated at about 80° C. for about 3.5 hours, cooled to room temperature and diluted with saturated aqueous NaHCO3 (2 L). The toluene layer was separated and washed with saturated aqueous NaCl, dried over Na2SO4 and concentrated in vacuo to give an oil (754.8 g). Crystallization from methanol/water afforded the desired product as a white solid (609.5 g). 1H-NMR (CDCl3) δ 1.50 (s, 9H), 2.53 (d, 1H), 2.70 (br s, 2H), 2.88 (br s, 1H), 3.31 (m, 2H), 3.97 (m, 1H), 4.19 (m, 1H), 4.46 (br s, 1H), 4.63 (br s, 1H), 7.06 (m, 2H), 7.51 (m, 1H), 8.34 (m, 1H).

Workup

  1. extractionanother toluene extraction of 70% aqueous 2,2,2-trifluoroethyl hydrazine (50 g)
  2. additionwas added
  3. temperatureThe reaction mixture was heated at about 80° C. for about 3.5 hours
  4. temperaturecooled to room temperature
  5. additiondiluted with saturated aqueous NaHCO3 (2 L)
  6. customThe toluene layer was separated
  7. washwashed with saturated aqueous NaCl
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-2b2927917f1649a0831e4b1345dbb262
Source dataset
uspto-grants-2003_10
Patent number
US06630487B2

Reaction notes

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